CA2110099C - Pigments whose color depends on the viewing angle, their preparation and use - Google Patents
Pigments whose color depends on the viewing angle, their preparation and useInfo
- Publication number
- CA2110099C CA2110099C CA002110099A CA2110099A CA2110099C CA 2110099 C CA2110099 C CA 2110099C CA 002110099 A CA002110099 A CA 002110099A CA 2110099 A CA2110099 A CA 2110099A CA 2110099 C CA2110099 C CA 2110099C
- Authority
- CA
- Canada
- Prior art keywords
- resins
- pigment
- pigments
- liquid
- substances
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 46
- 239000000975 dye Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- -1 polypropylene Polymers 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000180 alkyd Polymers 0.000 claims description 4
- 229920003180 amino resin Polymers 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920013716 polyethylene resin Polymers 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000976 ink Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000005018 casein Substances 0.000 claims description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021240 caseins Nutrition 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 2
- 125000005375 organosiloxane group Chemical group 0.000 claims 2
- 229920006218 cellulose propionate Polymers 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000004973 liquid crystal related substance Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 6
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 5
- 239000008240 homogeneous mixture Substances 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 4
- 229960004279 formaldehyde Drugs 0.000 description 4
- 235000019256 formaldehyde Nutrition 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000001056 green pigment Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000012000 cholesterol Nutrition 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- ZPFUEBYGWHYVMV-UHFFFAOYSA-N (4-ethylphenyl) 2-(2-methylprop-2-enoyloxy)benzoate Chemical compound C1=CC(CC)=CC=C1OC(=O)C1=CC=CC=C1OC(=O)C(C)=C ZPFUEBYGWHYVMV-UHFFFAOYSA-N 0.000 description 2
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 239000011243 crosslinked material Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229940044603 styrene Drugs 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XBBGNZAGYVHGRH-UHFFFAOYSA-N (4-ethylphenyl) 4-hydroxybenzoate Chemical compound C1=CC(CC)=CC=C1OC(=O)C1=CC=C(O)C=C1 XBBGNZAGYVHGRH-UHFFFAOYSA-N 0.000 description 1
- JDVZMYYRCZTOJV-UHFFFAOYSA-N (4-ethylphenyl) 4-trimethylsilyloxybenzoate Chemical compound C1=CC(CC)=CC=C1OC(=O)C1=CC=C(O[Si](C)(C)C)C=C1 JDVZMYYRCZTOJV-UHFFFAOYSA-N 0.000 description 1
- OWNPKCXSSRBDRY-UHFFFAOYSA-N (4-trimethylsilyloxyphenyl) 4-prop-2-enoxybenzoate Chemical compound C1=CC(O[Si](C)(C)C)=CC=C1OC(=O)C1=CC=C(OCC=C)C=C1 OWNPKCXSSRBDRY-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- LXSNYSIAVQLGQW-UHFFFAOYSA-N 11-(2-methylprop-2-enoyloxy)undecanoic acid Chemical compound CC(=C)C(=O)OCCCCCCCCCCC(O)=O LXSNYSIAVQLGQW-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- DTJGMNVTTPUVFY-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butanoic acid Chemical compound CC(=C)C(=O)OCCCC(O)=O DTJGMNVTTPUVFY-UHFFFAOYSA-N 0.000 description 1
- DYDWKSVZHZNBLO-UHFFFAOYSA-N 4-prop-2-enoxybenzoic acid Chemical compound OC(=O)C1=CC=C(OCC=C)C=C1 DYDWKSVZHZNBLO-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZHNSYNYLKYUVAH-GTPODGLVSA-N [(3s,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] 2-methylprop-2-enoate Chemical compound C1C=C2C[C@@H](OC(=O)C(C)=C)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 ZHNSYNYLKYUVAH-GTPODGLVSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0295—Liquid crystals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
- C09K19/406—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing silicon
- C09K19/408—Polysiloxanes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
- A61K2800/436—Interference pigments, e.g. Iridescent, Pearlescent
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Crystallography & Structural Chemistry (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to pigments whose color depends on the viewing angle, their preparation and use.
These pigments comprise oriented three-dimensionally cross-linked substances of liquid-crystalline structure having a chiral phase and, if desired, further dyes and pigments, the further dyes and pigments if present not serving as base for the oriented three-dimensionally crosslinked liquid-crystalline substances having a chiral phase.
These pigments comprise oriented three-dimensionally cross-linked substances of liquid-crystalline structure having a chiral phase and, if desired, further dyes and pigments, the further dyes and pigments if present not serving as base for the oriented three-dimensionally crosslinked liquid-crystalline substances having a chiral phase.
Description
Docket: CO 9208 Paper No. 1 PIGMENTS WHOSE COLOR D~ ON THE vl~wlNG ANGLE, THEIR PREPARATION AND USE
Field of Invention The invention relates to pigments whose color depends on the viewing angle, their preparation and use.
Background of Invention The most widely used prior art pigments consist of particles which absorb a portion of the incoming light and reflect the remainder. The reflected portion of the light deter~ines the color impression.
In addition there are pigments whose color is due to interfer-ence effects. These pigments are known as pearl luster pigments.
They consist of a base material, most frequently mica platelets, to which thin layers of substances having different optical densi-ties have been applied. These layers often consist of heavy metal compounds (Ullmanns Encyclopadie der technischen Chemie, 4th edition, 1976, Volume 18, p. 631 - 634). The application of pearl luster pigments containing heavy metals is problematic for reasons of environmental pollution during processing and disposal.
EP-A 383,376 describes the use of cholesteric liquid crystals instead of heavy metal compounds for coating mica platelets and other organic and inorganic base materials. While it is true that the use of cholesteric liquid crystals avoids the disadvantage of coatings containing heavy metals, the base materials themselves often contain heavy metals. Moreover, the above mentioned pig-ments must be able to meet processing and application parameters.
For example, the base material must not exceed a particular thickness otherwise the preparation of finely divided pigments is hampered. It is true that the base materials are very thin in the case where mica or metal flakes are used, but they need to be coated on the front and back in layer thicknesses to be strictly maintained.
SummarY of the Invention The object of the invention is to provide pigments which avoid the disadvantages of the prior art and make it possible to achieve novel color effects by means of circularly polarized light.
The object is achieved by pigments whose color depends on the viewing angle and comprise oriented three-dimensionally cross-linked substances of liquid-crystalline structure having a chiral phase and, if desired, further dyes and pigments, the further dyes and pigments if present not serving as base for the oriented three-dimensionally crosslinked liquid-crystalline substances having a chiral phase.
For the purposes of the invention, color is not only understood to mean the color impression of the wavelength region of visible light perceivable by the human eye but also the color impression of the adjacent W and IR wavelength regions not perceivable by the human eye but measurable by known instruments, such as W and IR spectrometers.
In one embodiment, the pigments according to the invention exclusively comprise an interference layer, this interference layer being composed of oriented three-dimensionally crosslinked liquid-crystalline substances having a chiral phase. Accordingly, the color of these pigments resides inclusively in an interference effect. The light reflected by these pigments is circularly polarized.
In another embodiment, the pigments according to the invention contain, in addition to the oriented three-dimensionally cross-linked liquid-crystalline substances having a chiral phase, other dyes or pigments. Suitable dyes are soluble in the unpolymerized starting substances for preparing the pigments according to the invention. Suitable additional pigments are miscible with the unpolymerized starting substances for preparing the pigments according to the invention. In this embodiment, the angle-depen-dent color effects of the pigments according to the invention have been combined with additional color effects of known pigments and dyes. Additional pigments which are free of heavy metals are particularly suitable. If the pigments according to the invention contain, for example, carbon black, the unreflected portion of the incoming light is absorbed in the pigment. The desired color impression of the pigments is not impaired by background reflec-tion if it occurs.
The pigments according to the invention do not contain any base material to which the oriented three-dimensionally crosslinked liquid-crystalline substances having a chiral phase have been applied.
The pigments according to the invention can be mixed with one another as desired. This makes it possible for the first time to produce any desired color effects varying with the viewing angle by means of liquid-crystalline substances by simple mixing and thus to obtain colors other than pure spectral color by means of liquid-crystalline substances. Thus, by mixing pigments according to the invention, it is possible for the first time to produce, for example, purple hues by means of liquid-crystalline sub-stances.
-The pigments according to the invention are obtainable by orienting three-dimensionally crosslinkable liquid-crystalline substances having a chiral phase, optionally admixing further dyes and/or pigments, crosslinking the liquid crystalline substances three-dimensionally and comminuting them to the desired particle size.
The three-dimensionally crosslinkable liquid-crystalline sub-stances having a chiral phase are preferably applied to a backing, crosslinked on this backing and removed from the backing after crosslinking.
Liquid-crystalline substances which are suitable as starting substances for preparing the pigments according to the invention have a twisted structure whose pitch corresponds to the wavelength of light in the region of UV to IR. This structure is encoun-tered, for example, in cholesteric liquid crystals. Cholesteric liquid crystals or in general liquid crystalline substances having a chiral phase and a twisted structure of the desired pitch can be obtained from nematic, smectic or discotic structures by adding a chiral substance to them. Type and amount of the chiral substance determine the pitch of the twisted structure and thus the wave-length of the reflected light. The twisting of the structure can be left- or right-handed. In addition, the starting substances must contain groups which can be subjected to condensation poly-merization or addition polymerization, at least some of which are present in the form of difunctional, trifunctional or higher functional building blocks. Examples of such groups are methacry-A ~o~loxy and acryloy~ groups.
Suitable materials and their preparation are described, for example, in DE-C2-3,604,757, EP-A2-358,208, EP-A0 066 137 (corre-sponding U.S. 4,388,453, issued on June 14, 1983) or in the 211~099 references in D.J. Broer et al., in 14. Int. Liquid Conf., Abstracts II, 921 (1992). Three-dimensionally crosslinkable polyorganosiloxanes according to EP-A-358,208 are preferred. In principle, any cholesteric liquid crystals can serve as starting materials for preparing the pigments according to the invention.
A single type of cholesteric liquid crystal or a mixture of these liquid crystals can be used. A dye or mixtures of dyes can be used.
In a preferred embodiment, the dye to be used is a pigment. In a further preferred embodiment, the dye to be used in the process according to the invention is soluble in the liquid crystal (mix-ture) used. In the process according to the invention, an indi-vidual pure cholesteric liquid-crystalline substance is preferably used.
Admixing of the pigments and/or dyes to the other starting substances takes place in the usual manner, for example by adding them with stirring. In the pigment according to the invention, admixing of the dyes and/or pigments results in a combination of angle-dependent color effects of the liquid-crystalline substances with the known color effect(s) of the substances admixed in each case. However, admixture of these substances does not change anything in the further process steps for preparing the pigments according to the invention.
The pigment color desired in a particular case may also be obtained by mixing defined liquid crystal base mixtures in suit-able weight ratios. In this case, too, the further process steps for preparing the pigments according to the invention are not changed thereby. The further description of the preparation pro-cess therefore applies to all variants of the pigments according to the invention.
Liquid crystals containing twisted phases do not develop their optical characteristics until the individual molecules are arranged in layers and are uniformly ordered within a layer. The molecules change their preferred direction from layer to layer, as a result of which helix-like structures are formed. To achieve this, the molecules are oriented by means of known methods, such as, for example, by means of orientation layers or electric or magnetic fields. Such methods are known, for example, from the following references: CA113 (22), 201523y; CA113 (14), 124523u;
CA112 (18), 169216s; CA112 (16), 149138q; CA112 (4), 21552c; CAlll (16), 144258y; CA111 (4), 24780r.
To prepare the pigments according to the invention, the start-ing substances mentioned are oriented in a known manner. This can be accomplished, for example, by knife-coating them onto a backing made of metal, plastic or glass. This backing can have been pro-vided, if desired, with an orientation layer made of, for example, polyimide or polyvinyl alcohol. They may also have been silanized for this purpose. However, it is also possible to shear the starting substance between two sheets. Preferably, one or two polyethylene terephthalate sheets are used.
Knife-coating or liquid-crystalline polyorganosiloxanes onto a sheet is known, for example from EP-A-358,208.
Crosslinking of the oriented liquid-crystalline substances is carried out as disclosed for the material in question from the prior art. Thus, for example, liquid-crystalline polyorganosi-loxanes can be crosslinked thermally by the method described in EP-A-66,137. The liquid-crystalline polyorganosiloxanes described D ~
D in ~ -A-358,208 can be crosslinked three-dimensionally by photo-chemical means, for example by irradiation with W light. A
~~~survey of methods of crosslinking oriented starting materials photochemically can be found in C.G. Roffey, Photopolymerization of Surface Coatings, (1982) John Willey & Sons, Chichester, p.
137-208.
The crosslinked oriented liquid-crystalline substances having a chiral phase are, if desired, removed from the backing. If a sheet is used as the backing, mechanical removal of the brittle crosslinked liquid crystals from the backing can be accomplished, for example, by guiding the backing over a deflecting roller of small diameter. This results in the crosslinked material being peeled off from the sheet. However, any other method by which the polymerized material can be removed from the backing is also suitable.
The oriented three-dimensionally crosslinked support-free liquid-crystalline material is comminuted to the particle size desired in each case. This can be effected, for example, by milling in universal mills. Depending on the desired application of the pigments, particle sizes having a diameter of about 10 mm up to one ~m can be prepared. Preferably the pigments have a particle size of between 5 mm and 5 ~m. The pigments have a thickness of between 1 and 100 ~m, preferably 5 to 50 ~m.
In order to narrow the particle size distribution, the mill base can then be classified, for example by screening.
The pigments according to the invention are suitable for col-oring a wide range of materials, such as paints and coatings, plastics, fiber raw materials, cosmetics or printing inks of any type, for example screen printing inks. To this end, the pigments are incorporated in the particular material like known pigments.
The corresponding pigment-containing compositions thus prepared exhibit the same coloristic properties described for the pigments themselves.
The invention also relates to compositions containing at least one pigment according to the invention. They are in particular compositions which comprise, apart from the pigments according to the invention at least one substance from the group consisting of phenolic resins, amino resins, alkyd resins, polyvinyl acetate resins, epoxy resins, polyurethane resins, polyethylene resins, chlorinated rubber resins, cyclorubber resins, chlorinated poly-propylene, ketone resins, acrylate resins, melamine resins, urea-formaldehyde resins, phenol/formaldehyde resins or at least one substance from the group comprising acrylonitrile/butadiene/sty-rene copolymers, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate, cellulose nitrate, cellulose propio-nate, casein plastics, polyamide, polycarbonate, polyethylene, polybutylene terephthalate, polymethyl methacrylate, polypropy-lene, polystyrene, polytetrafluoroethylene, polyvinyl chloride, polyvinylidene chloride, polyurethane, styrene/acrylonitrile copolymers, unsaturated polyester resins.
The above mentioned compositions enable novel color effects to be produced, particularly in combination with smooth curved sur-faces. These surfaces appear to be intrinsically differently colored. This different coloring changes depending on the loca-tion of the observer.
Compositions according to the invention comprising at least one substance from the group comprising phenolic resins, amino resins, alkyd resins, polyvinyl acetate resins, epoxy resins, polyureth-ane resins, polyethylene resins, chlorinated rubber resins, cyclo-rubber resins, chlorinated polypropylene, ketone resins, acrylate 21100~9 resins, melamine resins, ureaformaldehyde resins, phenol/formalde-hyde resins, and about 10% by weight (relative to the total weight) of the pigments according to the invention exhibit, after being applied to a black metal sheet high color brilliance and a varying color impression depending on the viewing angle. The reflected light is circularly polarized. Even if the liquid-crystalline polyorganosiloxane pigment incorporated in the compo-sition is used in particle sizes of less than 25 ~m, the high color brilliance and the varying color impression depending on the viewing angle are maintained.
Compositions comprising at least one pigment according to the invention and one substance from the group comprising phenolic resins, amino resins, alkyd resins, polyvinyl acetate resins, epoxy resins, polyurethane resins, polyethylene resins, chlori-nated rubber resins, cyclorubber resins, chlorinated polypropy-lene, ketone resins, acrylate resins, melamine resins, urea/for-maldehyde resins, phenol/formaldehyde resins are suitable in par-ticular for coating metallic surfaces. If such compositions are used for coating automobiles, a passing automobile thus coated appears to an observer in various colors. These colors can be adjusted as desired by suitable selection of the pigments used.
The pigments according to the invention are furthermore suit-able as security marking. Thus, for example, paints, coatings and sheets containing pigments according to the invention which show reflection in the W or IR region can be used as markings and security marks invisible to the human eye. They can be detected via polarization or angle dependence of the reflected or trans-mitted light.
Figure 1 shows the viewing described in Example 7 of a surface coated with a lacquer containing pigments according to the inven-211009~
tion. In this figure, 1 is the light source; 2 the viewer; 3 the coated surface; ~ the angle of the incident light, i.e., the angle between the normal surface and the light source; ~ is the viewing angle, i.e., the angle between the normal surface and the observer.
The examples which follow serve to further illustrate the invention.
Example 1 A: Polyorganosiloxanes having side chains containing methacrylic acid -A solution of 233 g of cholesterol 4-(prop-2-en-1-oxy)benz-oate (obtainable according to DE-A 3,110,048), 178 g of 4-tri-methylsiloxyphenyl 4-(prop-2-en-1-oxy)-benzoate (obtainable according to EP-A-358,208, page 9, section C) and 56.9 g of tetramethylcyclotetrasiloxane in 400 ml of toluene were refluxed in the presence of 24 mg of dicyclopentadieneplatinum dichloride for 1 hour and, after addition of a solution of 1.2 g of NaOH in 50 ml of ethanol, for another 7 hours in order to effect cleavage of the silyl ether. The reaction mixture was concentrated to 1/3 of its volume in a rotary evaporator, 7.5 g of p-toluenesulfonic acid and 154 g of methacrylic anhydride were added, and the mixture was heated at 100C for 1 hour.
After the volatile components had been distilled off, the residue was reprecipitated twice with methylene chloride/
ethanol.
The product had the following physical and thermodynamic data: glass transition temperature: 14C, clearing point:
141C.
B. Preparation of a pigment -4 g of the polyorganosiloxane prepared as described in A
were heated to 70C and mixed with 0.11 g of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone (obtainable under B the name Irgacure 907 from Ciba Marienberg GmbH, 6140 Bensheim 1) with stirring until a homogeneous mixture was obtained.
This gave a viscous liquid crystal (LC) composition having a reddish shimmer. The liquid-crystalline material was knife-coated at 120C onto a polyethylene terephthalate sheet (Hoechst AG, Geschaftsbereich Folien, 6200 Wiesbaden 1) in layer thicknesses of 15 ~m, during which the sheet was advanced under the fixed knife at a running speed of about 2 m/min.
This simultaneously led to orientation of the liquid-crystal-line molecules owing to the shearing gradient between knife and sheet, which became visible by red coloring of the liquid crystal layer. This layer was then irradiated using a mercury discharge lamp (80 W/cm) for 5 seconds and thus crosslinked three-dimentionally. The film produced on the sheet was non-tacky and brittle in the heat and the cold. It had a reflec-tion wavelength of 560 nm. (Angle of incidence and viewing angle 45, see Figure 1). Mechanical removal of the liquid-crystalline material obtained in this manner from the backing was accomplished by leading the sheet over a deflecting roller 10 cm in diameter, as a result of which the crosslinked material peels off from the support. Milling of the cross-linked, substrate-free material was carried out in a universal mill. Milling of the crosslinked polyorganosiloxanes predomi-nantly present in the form of leaflets for 5 minutes gave a pulverulent fraction. In order to narrow the particle size 7~ s 7L~ Qrk distribution, the mill base was then subjected to a screening process. To this end, the milled pigments were screened by means of an analytical screen having a mesh size of 100 ~m.
Example 2 A. Preparation of a blue liquid crystal mixture -As described in Example 1, 6 g of the polyorganosiloxane were prepared. It was dissolved in 50 ml of toluene. 2.6 g of cholesterol methacrylate (prepared as described in De Visser et al., J. Polym, Sci., A 1(9), 1893 (1971)) and 9 mg of aluminum ~, c c~f~r-o ~, 10 ~ p'f~l~n (obt~;nAble under the name Q1301 from Wako Chemicals GmbH, 4040 Neuss) were added to the solution. The toluene was then removed at 70OC in vacuo in a rotary evaporator to give a viscous LC composition having the following physical and ther-modynamical data: glass transition temperature: 4 C, clear point: 132C.
B. Preparation of a pigment -4 g of the LC composition prepared as described in A were heated to 70C, and mixed with 0.11 g of 2-methyl-1-(4-(methylthio)phenyl)-2-morpholino-1-propanone (obtainable under the name Irgacure 907 from Ciba Marienberg GmbH, 6140 Bensheim 1) with stirring until a homogeneous mixture was obtained. The liquid-crystalline material was further processed as described in Example 1 under B, except it was applied to the sheet at a temperature of 80C and crosslinked photochemically. The film produced on the sheet had a reflection wavelength of 400 nm.
The pigments had an intensely blue color.
Example 3 A Preparation of a polymerizable monomer: 4-Ethylphenyl meth-acryloxybenzoate -2110~99 A solution of 16.9 g of 4-ethylphenyl 4-trimethylsilyloxy-benzoate (prepared by the procedure in EP-A-358,208, page 9, sec. C) in 15 ml of toluene and 10 ml of ethanol was refluxed for 1 hour and then freed from volatile components by heating at 100C for 60 minutes. The remaining 13.3 g of 4-ethylphenyl 4-hydroxybenzoate were dissolved in 15 ml of toluene together with 30 g of methacrylic anhydride and 1.2 g of toluenesulfonic acid, and the mixture was heated at lOO-C for 1 hour. After cooling, the product was precipitated with hexane and recry-stallized from ethanol.
B. Preparation of a red liquid crystal mixture -6 g of the polyorganosiloxane prepared as in Example lA were dissolved in 50 ml of toluene. 1.5 g of 4-ethylphenyl meth-acryloxybenzoate (prepared as in Example 3A) and 7.5 mg of C ~p~c r ~ ~
B aluminum cu~fcron (obtainable under the name A 1301 from Wako Chemicals GmbH, 4040 Neuss) were added to the solution. The toluene was then removed at 70C in vacuo in a rotary evapora-tor.
This gives a viscous LC composition having the following physical and thermodynamical data: glass transition tempera-ture: -2C, clearing point: 124C.
C. Preparation of a pigment -The mixture thus obtained was treated as described in Exam-ple 2B. The film produced on the sheet had a reflection wave-length of 630 nm. The pigments obtained have an intensely red color.
211~099 -Example 4 A. Preparation of a green liquid crystal mixture -2.8 g of the red-colored mixture (prepared as described in Example 3B), 1.2 g of the blue-colored mixture (prepared as described in Example 2A) and 0.11 g of 2-methyl-1-[4-methyl-thio)phenyl]-2-morpholino-1-propanone (obtainable under the name Irgacure 907 from Ciba Marienberg GmbH, 6140 Bensheim 1) were mixed with stirring until a homogeneous mixture was obtained. This gives a viscous LC composition having a green-ish shimmer and the following thermodynamic data: glass transi-tion temperature: 2C, clearing point: 128C.
B. Preparation of a pigment -The mixture thus obtained was further processed as described in Example 2B by applying it to a sheet at a temperature of 80C and crosslinking it photochemically. The film produced on the sheet had a reflection wavelength of 530 nm. The pigments obtained have an intensely green color.
Example 5 A Preparation of a green liquid crystal mixture -A homogeneous mixture having a green shimmer was prepared from 2 g of cholesterol 11-methacryloxyundecanoate (prepared according to P.J. Shannon et al., Macromolecules, 1984, 17, 1873-1876;) 2 g of cholesterol 4-methacryloxybutyrate (prepared according to P.J. Shannon et al., Macromolecules, 1984, 17, 1873-1876;) and 0.1 g of hexanediol diacrylate (obtainable from Janssen Chimica, 40S7 Bruggen 2) by heating to 50 C and stirring.
B. Preparation of a pigment -The mixture thus obtained was further processed as described in Example 2B (temperature of the sheet: 30 C) to give pigments having an intensely green color.
Example 6 Preparation of a pigment containing carbon black -0.2 g of FWl(HCC) carbon black (Degussa, Frankfurt) were incorporated in 10 g of a mixture obtained as in Example 4A
with stirring until a homogeneous mixture was obtained. The mixture thus obtained was further processed as described in Example 2B to give pigments having an intensely green color even on a white ground.
Example 7 Preparation and use of a coating containing green pigments -1 g of the pigment fraction prepared in Example 4 (particle size < 100 ~m) was dispersed for 5 minuted with stirring in 2 g 15 B of thinner (Permacron Supercryl, Verdunnung 3054, Spies and Hecker, 5000 Cologne). This dispersion was added to a mixture of 5 g of a clear coating (Permacron MS Klarlack 8010, Spies and Hecker) and 2.5 g of curing agent (Permacron MS Spezial Harter 3368, Spies and Hecker). The coating formulation thus obtained was evenly sprayed onto a metal sheet provided with a black base (size: 20 x 25 cm) in the form of fine droplets using a paint spray gun (Sata-Farbspritz~chn;k GmbH, Ludwigs-burg). After coating, the metal sheet was pre-dried at 80C
for 10 minutes, and a clear coat (coating formulation as described but without pigments) was applied twice as a protec-tive layer.
The resulting metal sheet exhibits a green color of high brilliance at small angles a and ~ (Fig. 1). With increasing angles a and ~, the green color continuously changes to a blue ~dc~ s ~J~
color. Accordingly, on curved surfaces and in the presence of diffuse, non-directional light, a plurality of colors between green and blue are simultaneously visible depending on the viewing angle.
Example 8 Preparation and use of a coating containing mixtures of pig-ments according to the invention -1 g of blue pigment prepared as described in Example 2 and 1 g of red pigment prepared as described in Example 3 were dis-persed in 4 g of thinner for 5 minutes with stirring, further processed as described in Example 7, and sprayed onto a metal sheet provided with a black base. The metal sheet was given a clear coat protective layer as described in Example 7. A
purple color of high brilliance is observed for small values of ~ and ~, which with increasing angles ~ and ~ continuously changes to a turquoise-like color.
Example 9 Determination of the polarization of the reflected light -Upon viewing the metal sheet coated according to Example 4 through a polarizer for left circularly polarized or right circularly polarized light, the reflection color is visible in the first case but the metal sheet appears black in the second case.
Example 10 Incorporation of gree~ pigments in rigid PVC -9o parts by weight of rigid PVC (obtainable from Wacker-B Chemie GmbH, Munich under the name Vinnol H 70 F), 10 parts by weight of bis(2-ethylhexyl) phthalate (Janssen Chimica, 4057 Bruggen 2), 2 parts by weight of Hostastab SnOS 661 (Hoechst e h o7~s ~r~ ~ Q~-k AG, Frankfurt), 1 part of partially saponified ester wax obtained from montan acid (Wachs OP; Hoechst AG, Frankfurt) and 10 parts by weight of green pigments from Example 4 were com-bined and homogenized for 10 minutes at 150C and a friction of S 1:1.1 using a roll. The resulting composition was processed ina press at 170-C to give sheets. The sheets exhibit the same green-blue color effects as the coated metal sheet described in the prec~;ng examples.
Example 11 Incorporation of green pigments in plasticized PVC -100 parts by weight of plasticized PVC (obt~in~hle from Wacker-Chemie GmbH Munich under the name Vinnol P 70), 50 parts by weight of bis(2-ethylhexyl) phthalate, 1 part of barium/zinc B stabilizer (obtainable as Irgastab BZ 505 from Ciba AG, Basle)and 7.5 parts by weight of the green pigments prepared accord-ing to Example 4 were combined, homogenized and poured onto a glass plate. After 10 minutes of gelling in a drying cabinet at 180-C, a transparent film is obtained which exhibits an angle-dependent color effect as described in the prece~;ng examples.
~ > o7'~s ~r~ k
Field of Invention The invention relates to pigments whose color depends on the viewing angle, their preparation and use.
Background of Invention The most widely used prior art pigments consist of particles which absorb a portion of the incoming light and reflect the remainder. The reflected portion of the light deter~ines the color impression.
In addition there are pigments whose color is due to interfer-ence effects. These pigments are known as pearl luster pigments.
They consist of a base material, most frequently mica platelets, to which thin layers of substances having different optical densi-ties have been applied. These layers often consist of heavy metal compounds (Ullmanns Encyclopadie der technischen Chemie, 4th edition, 1976, Volume 18, p. 631 - 634). The application of pearl luster pigments containing heavy metals is problematic for reasons of environmental pollution during processing and disposal.
EP-A 383,376 describes the use of cholesteric liquid crystals instead of heavy metal compounds for coating mica platelets and other organic and inorganic base materials. While it is true that the use of cholesteric liquid crystals avoids the disadvantage of coatings containing heavy metals, the base materials themselves often contain heavy metals. Moreover, the above mentioned pig-ments must be able to meet processing and application parameters.
For example, the base material must not exceed a particular thickness otherwise the preparation of finely divided pigments is hampered. It is true that the base materials are very thin in the case where mica or metal flakes are used, but they need to be coated on the front and back in layer thicknesses to be strictly maintained.
SummarY of the Invention The object of the invention is to provide pigments which avoid the disadvantages of the prior art and make it possible to achieve novel color effects by means of circularly polarized light.
The object is achieved by pigments whose color depends on the viewing angle and comprise oriented three-dimensionally cross-linked substances of liquid-crystalline structure having a chiral phase and, if desired, further dyes and pigments, the further dyes and pigments if present not serving as base for the oriented three-dimensionally crosslinked liquid-crystalline substances having a chiral phase.
For the purposes of the invention, color is not only understood to mean the color impression of the wavelength region of visible light perceivable by the human eye but also the color impression of the adjacent W and IR wavelength regions not perceivable by the human eye but measurable by known instruments, such as W and IR spectrometers.
In one embodiment, the pigments according to the invention exclusively comprise an interference layer, this interference layer being composed of oriented three-dimensionally crosslinked liquid-crystalline substances having a chiral phase. Accordingly, the color of these pigments resides inclusively in an interference effect. The light reflected by these pigments is circularly polarized.
In another embodiment, the pigments according to the invention contain, in addition to the oriented three-dimensionally cross-linked liquid-crystalline substances having a chiral phase, other dyes or pigments. Suitable dyes are soluble in the unpolymerized starting substances for preparing the pigments according to the invention. Suitable additional pigments are miscible with the unpolymerized starting substances for preparing the pigments according to the invention. In this embodiment, the angle-depen-dent color effects of the pigments according to the invention have been combined with additional color effects of known pigments and dyes. Additional pigments which are free of heavy metals are particularly suitable. If the pigments according to the invention contain, for example, carbon black, the unreflected portion of the incoming light is absorbed in the pigment. The desired color impression of the pigments is not impaired by background reflec-tion if it occurs.
The pigments according to the invention do not contain any base material to which the oriented three-dimensionally crosslinked liquid-crystalline substances having a chiral phase have been applied.
The pigments according to the invention can be mixed with one another as desired. This makes it possible for the first time to produce any desired color effects varying with the viewing angle by means of liquid-crystalline substances by simple mixing and thus to obtain colors other than pure spectral color by means of liquid-crystalline substances. Thus, by mixing pigments according to the invention, it is possible for the first time to produce, for example, purple hues by means of liquid-crystalline sub-stances.
-The pigments according to the invention are obtainable by orienting three-dimensionally crosslinkable liquid-crystalline substances having a chiral phase, optionally admixing further dyes and/or pigments, crosslinking the liquid crystalline substances three-dimensionally and comminuting them to the desired particle size.
The three-dimensionally crosslinkable liquid-crystalline sub-stances having a chiral phase are preferably applied to a backing, crosslinked on this backing and removed from the backing after crosslinking.
Liquid-crystalline substances which are suitable as starting substances for preparing the pigments according to the invention have a twisted structure whose pitch corresponds to the wavelength of light in the region of UV to IR. This structure is encoun-tered, for example, in cholesteric liquid crystals. Cholesteric liquid crystals or in general liquid crystalline substances having a chiral phase and a twisted structure of the desired pitch can be obtained from nematic, smectic or discotic structures by adding a chiral substance to them. Type and amount of the chiral substance determine the pitch of the twisted structure and thus the wave-length of the reflected light. The twisting of the structure can be left- or right-handed. In addition, the starting substances must contain groups which can be subjected to condensation poly-merization or addition polymerization, at least some of which are present in the form of difunctional, trifunctional or higher functional building blocks. Examples of such groups are methacry-A ~o~loxy and acryloy~ groups.
Suitable materials and their preparation are described, for example, in DE-C2-3,604,757, EP-A2-358,208, EP-A0 066 137 (corre-sponding U.S. 4,388,453, issued on June 14, 1983) or in the 211~099 references in D.J. Broer et al., in 14. Int. Liquid Conf., Abstracts II, 921 (1992). Three-dimensionally crosslinkable polyorganosiloxanes according to EP-A-358,208 are preferred. In principle, any cholesteric liquid crystals can serve as starting materials for preparing the pigments according to the invention.
A single type of cholesteric liquid crystal or a mixture of these liquid crystals can be used. A dye or mixtures of dyes can be used.
In a preferred embodiment, the dye to be used is a pigment. In a further preferred embodiment, the dye to be used in the process according to the invention is soluble in the liquid crystal (mix-ture) used. In the process according to the invention, an indi-vidual pure cholesteric liquid-crystalline substance is preferably used.
Admixing of the pigments and/or dyes to the other starting substances takes place in the usual manner, for example by adding them with stirring. In the pigment according to the invention, admixing of the dyes and/or pigments results in a combination of angle-dependent color effects of the liquid-crystalline substances with the known color effect(s) of the substances admixed in each case. However, admixture of these substances does not change anything in the further process steps for preparing the pigments according to the invention.
The pigment color desired in a particular case may also be obtained by mixing defined liquid crystal base mixtures in suit-able weight ratios. In this case, too, the further process steps for preparing the pigments according to the invention are not changed thereby. The further description of the preparation pro-cess therefore applies to all variants of the pigments according to the invention.
Liquid crystals containing twisted phases do not develop their optical characteristics until the individual molecules are arranged in layers and are uniformly ordered within a layer. The molecules change their preferred direction from layer to layer, as a result of which helix-like structures are formed. To achieve this, the molecules are oriented by means of known methods, such as, for example, by means of orientation layers or electric or magnetic fields. Such methods are known, for example, from the following references: CA113 (22), 201523y; CA113 (14), 124523u;
CA112 (18), 169216s; CA112 (16), 149138q; CA112 (4), 21552c; CAlll (16), 144258y; CA111 (4), 24780r.
To prepare the pigments according to the invention, the start-ing substances mentioned are oriented in a known manner. This can be accomplished, for example, by knife-coating them onto a backing made of metal, plastic or glass. This backing can have been pro-vided, if desired, with an orientation layer made of, for example, polyimide or polyvinyl alcohol. They may also have been silanized for this purpose. However, it is also possible to shear the starting substance between two sheets. Preferably, one or two polyethylene terephthalate sheets are used.
Knife-coating or liquid-crystalline polyorganosiloxanes onto a sheet is known, for example from EP-A-358,208.
Crosslinking of the oriented liquid-crystalline substances is carried out as disclosed for the material in question from the prior art. Thus, for example, liquid-crystalline polyorganosi-loxanes can be crosslinked thermally by the method described in EP-A-66,137. The liquid-crystalline polyorganosiloxanes described D ~
D in ~ -A-358,208 can be crosslinked three-dimensionally by photo-chemical means, for example by irradiation with W light. A
~~~survey of methods of crosslinking oriented starting materials photochemically can be found in C.G. Roffey, Photopolymerization of Surface Coatings, (1982) John Willey & Sons, Chichester, p.
137-208.
The crosslinked oriented liquid-crystalline substances having a chiral phase are, if desired, removed from the backing. If a sheet is used as the backing, mechanical removal of the brittle crosslinked liquid crystals from the backing can be accomplished, for example, by guiding the backing over a deflecting roller of small diameter. This results in the crosslinked material being peeled off from the sheet. However, any other method by which the polymerized material can be removed from the backing is also suitable.
The oriented three-dimensionally crosslinked support-free liquid-crystalline material is comminuted to the particle size desired in each case. This can be effected, for example, by milling in universal mills. Depending on the desired application of the pigments, particle sizes having a diameter of about 10 mm up to one ~m can be prepared. Preferably the pigments have a particle size of between 5 mm and 5 ~m. The pigments have a thickness of between 1 and 100 ~m, preferably 5 to 50 ~m.
In order to narrow the particle size distribution, the mill base can then be classified, for example by screening.
The pigments according to the invention are suitable for col-oring a wide range of materials, such as paints and coatings, plastics, fiber raw materials, cosmetics or printing inks of any type, for example screen printing inks. To this end, the pigments are incorporated in the particular material like known pigments.
The corresponding pigment-containing compositions thus prepared exhibit the same coloristic properties described for the pigments themselves.
The invention also relates to compositions containing at least one pigment according to the invention. They are in particular compositions which comprise, apart from the pigments according to the invention at least one substance from the group consisting of phenolic resins, amino resins, alkyd resins, polyvinyl acetate resins, epoxy resins, polyurethane resins, polyethylene resins, chlorinated rubber resins, cyclorubber resins, chlorinated poly-propylene, ketone resins, acrylate resins, melamine resins, urea-formaldehyde resins, phenol/formaldehyde resins or at least one substance from the group comprising acrylonitrile/butadiene/sty-rene copolymers, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate, cellulose nitrate, cellulose propio-nate, casein plastics, polyamide, polycarbonate, polyethylene, polybutylene terephthalate, polymethyl methacrylate, polypropy-lene, polystyrene, polytetrafluoroethylene, polyvinyl chloride, polyvinylidene chloride, polyurethane, styrene/acrylonitrile copolymers, unsaturated polyester resins.
The above mentioned compositions enable novel color effects to be produced, particularly in combination with smooth curved sur-faces. These surfaces appear to be intrinsically differently colored. This different coloring changes depending on the loca-tion of the observer.
Compositions according to the invention comprising at least one substance from the group comprising phenolic resins, amino resins, alkyd resins, polyvinyl acetate resins, epoxy resins, polyureth-ane resins, polyethylene resins, chlorinated rubber resins, cyclo-rubber resins, chlorinated polypropylene, ketone resins, acrylate 21100~9 resins, melamine resins, ureaformaldehyde resins, phenol/formalde-hyde resins, and about 10% by weight (relative to the total weight) of the pigments according to the invention exhibit, after being applied to a black metal sheet high color brilliance and a varying color impression depending on the viewing angle. The reflected light is circularly polarized. Even if the liquid-crystalline polyorganosiloxane pigment incorporated in the compo-sition is used in particle sizes of less than 25 ~m, the high color brilliance and the varying color impression depending on the viewing angle are maintained.
Compositions comprising at least one pigment according to the invention and one substance from the group comprising phenolic resins, amino resins, alkyd resins, polyvinyl acetate resins, epoxy resins, polyurethane resins, polyethylene resins, chlori-nated rubber resins, cyclorubber resins, chlorinated polypropy-lene, ketone resins, acrylate resins, melamine resins, urea/for-maldehyde resins, phenol/formaldehyde resins are suitable in par-ticular for coating metallic surfaces. If such compositions are used for coating automobiles, a passing automobile thus coated appears to an observer in various colors. These colors can be adjusted as desired by suitable selection of the pigments used.
The pigments according to the invention are furthermore suit-able as security marking. Thus, for example, paints, coatings and sheets containing pigments according to the invention which show reflection in the W or IR region can be used as markings and security marks invisible to the human eye. They can be detected via polarization or angle dependence of the reflected or trans-mitted light.
Figure 1 shows the viewing described in Example 7 of a surface coated with a lacquer containing pigments according to the inven-211009~
tion. In this figure, 1 is the light source; 2 the viewer; 3 the coated surface; ~ the angle of the incident light, i.e., the angle between the normal surface and the light source; ~ is the viewing angle, i.e., the angle between the normal surface and the observer.
The examples which follow serve to further illustrate the invention.
Example 1 A: Polyorganosiloxanes having side chains containing methacrylic acid -A solution of 233 g of cholesterol 4-(prop-2-en-1-oxy)benz-oate (obtainable according to DE-A 3,110,048), 178 g of 4-tri-methylsiloxyphenyl 4-(prop-2-en-1-oxy)-benzoate (obtainable according to EP-A-358,208, page 9, section C) and 56.9 g of tetramethylcyclotetrasiloxane in 400 ml of toluene were refluxed in the presence of 24 mg of dicyclopentadieneplatinum dichloride for 1 hour and, after addition of a solution of 1.2 g of NaOH in 50 ml of ethanol, for another 7 hours in order to effect cleavage of the silyl ether. The reaction mixture was concentrated to 1/3 of its volume in a rotary evaporator, 7.5 g of p-toluenesulfonic acid and 154 g of methacrylic anhydride were added, and the mixture was heated at 100C for 1 hour.
After the volatile components had been distilled off, the residue was reprecipitated twice with methylene chloride/
ethanol.
The product had the following physical and thermodynamic data: glass transition temperature: 14C, clearing point:
141C.
B. Preparation of a pigment -4 g of the polyorganosiloxane prepared as described in A
were heated to 70C and mixed with 0.11 g of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone (obtainable under B the name Irgacure 907 from Ciba Marienberg GmbH, 6140 Bensheim 1) with stirring until a homogeneous mixture was obtained.
This gave a viscous liquid crystal (LC) composition having a reddish shimmer. The liquid-crystalline material was knife-coated at 120C onto a polyethylene terephthalate sheet (Hoechst AG, Geschaftsbereich Folien, 6200 Wiesbaden 1) in layer thicknesses of 15 ~m, during which the sheet was advanced under the fixed knife at a running speed of about 2 m/min.
This simultaneously led to orientation of the liquid-crystal-line molecules owing to the shearing gradient between knife and sheet, which became visible by red coloring of the liquid crystal layer. This layer was then irradiated using a mercury discharge lamp (80 W/cm) for 5 seconds and thus crosslinked three-dimentionally. The film produced on the sheet was non-tacky and brittle in the heat and the cold. It had a reflec-tion wavelength of 560 nm. (Angle of incidence and viewing angle 45, see Figure 1). Mechanical removal of the liquid-crystalline material obtained in this manner from the backing was accomplished by leading the sheet over a deflecting roller 10 cm in diameter, as a result of which the crosslinked material peels off from the support. Milling of the cross-linked, substrate-free material was carried out in a universal mill. Milling of the crosslinked polyorganosiloxanes predomi-nantly present in the form of leaflets for 5 minutes gave a pulverulent fraction. In order to narrow the particle size 7~ s 7L~ Qrk distribution, the mill base was then subjected to a screening process. To this end, the milled pigments were screened by means of an analytical screen having a mesh size of 100 ~m.
Example 2 A. Preparation of a blue liquid crystal mixture -As described in Example 1, 6 g of the polyorganosiloxane were prepared. It was dissolved in 50 ml of toluene. 2.6 g of cholesterol methacrylate (prepared as described in De Visser et al., J. Polym, Sci., A 1(9), 1893 (1971)) and 9 mg of aluminum ~, c c~f~r-o ~, 10 ~ p'f~l~n (obt~;nAble under the name Q1301 from Wako Chemicals GmbH, 4040 Neuss) were added to the solution. The toluene was then removed at 70OC in vacuo in a rotary evaporator to give a viscous LC composition having the following physical and ther-modynamical data: glass transition temperature: 4 C, clear point: 132C.
B. Preparation of a pigment -4 g of the LC composition prepared as described in A were heated to 70C, and mixed with 0.11 g of 2-methyl-1-(4-(methylthio)phenyl)-2-morpholino-1-propanone (obtainable under the name Irgacure 907 from Ciba Marienberg GmbH, 6140 Bensheim 1) with stirring until a homogeneous mixture was obtained. The liquid-crystalline material was further processed as described in Example 1 under B, except it was applied to the sheet at a temperature of 80C and crosslinked photochemically. The film produced on the sheet had a reflection wavelength of 400 nm.
The pigments had an intensely blue color.
Example 3 A Preparation of a polymerizable monomer: 4-Ethylphenyl meth-acryloxybenzoate -2110~99 A solution of 16.9 g of 4-ethylphenyl 4-trimethylsilyloxy-benzoate (prepared by the procedure in EP-A-358,208, page 9, sec. C) in 15 ml of toluene and 10 ml of ethanol was refluxed for 1 hour and then freed from volatile components by heating at 100C for 60 minutes. The remaining 13.3 g of 4-ethylphenyl 4-hydroxybenzoate were dissolved in 15 ml of toluene together with 30 g of methacrylic anhydride and 1.2 g of toluenesulfonic acid, and the mixture was heated at lOO-C for 1 hour. After cooling, the product was precipitated with hexane and recry-stallized from ethanol.
B. Preparation of a red liquid crystal mixture -6 g of the polyorganosiloxane prepared as in Example lA were dissolved in 50 ml of toluene. 1.5 g of 4-ethylphenyl meth-acryloxybenzoate (prepared as in Example 3A) and 7.5 mg of C ~p~c r ~ ~
B aluminum cu~fcron (obtainable under the name A 1301 from Wako Chemicals GmbH, 4040 Neuss) were added to the solution. The toluene was then removed at 70C in vacuo in a rotary evapora-tor.
This gives a viscous LC composition having the following physical and thermodynamical data: glass transition tempera-ture: -2C, clearing point: 124C.
C. Preparation of a pigment -The mixture thus obtained was treated as described in Exam-ple 2B. The film produced on the sheet had a reflection wave-length of 630 nm. The pigments obtained have an intensely red color.
211~099 -Example 4 A. Preparation of a green liquid crystal mixture -2.8 g of the red-colored mixture (prepared as described in Example 3B), 1.2 g of the blue-colored mixture (prepared as described in Example 2A) and 0.11 g of 2-methyl-1-[4-methyl-thio)phenyl]-2-morpholino-1-propanone (obtainable under the name Irgacure 907 from Ciba Marienberg GmbH, 6140 Bensheim 1) were mixed with stirring until a homogeneous mixture was obtained. This gives a viscous LC composition having a green-ish shimmer and the following thermodynamic data: glass transi-tion temperature: 2C, clearing point: 128C.
B. Preparation of a pigment -The mixture thus obtained was further processed as described in Example 2B by applying it to a sheet at a temperature of 80C and crosslinking it photochemically. The film produced on the sheet had a reflection wavelength of 530 nm. The pigments obtained have an intensely green color.
Example 5 A Preparation of a green liquid crystal mixture -A homogeneous mixture having a green shimmer was prepared from 2 g of cholesterol 11-methacryloxyundecanoate (prepared according to P.J. Shannon et al., Macromolecules, 1984, 17, 1873-1876;) 2 g of cholesterol 4-methacryloxybutyrate (prepared according to P.J. Shannon et al., Macromolecules, 1984, 17, 1873-1876;) and 0.1 g of hexanediol diacrylate (obtainable from Janssen Chimica, 40S7 Bruggen 2) by heating to 50 C and stirring.
B. Preparation of a pigment -The mixture thus obtained was further processed as described in Example 2B (temperature of the sheet: 30 C) to give pigments having an intensely green color.
Example 6 Preparation of a pigment containing carbon black -0.2 g of FWl(HCC) carbon black (Degussa, Frankfurt) were incorporated in 10 g of a mixture obtained as in Example 4A
with stirring until a homogeneous mixture was obtained. The mixture thus obtained was further processed as described in Example 2B to give pigments having an intensely green color even on a white ground.
Example 7 Preparation and use of a coating containing green pigments -1 g of the pigment fraction prepared in Example 4 (particle size < 100 ~m) was dispersed for 5 minuted with stirring in 2 g 15 B of thinner (Permacron Supercryl, Verdunnung 3054, Spies and Hecker, 5000 Cologne). This dispersion was added to a mixture of 5 g of a clear coating (Permacron MS Klarlack 8010, Spies and Hecker) and 2.5 g of curing agent (Permacron MS Spezial Harter 3368, Spies and Hecker). The coating formulation thus obtained was evenly sprayed onto a metal sheet provided with a black base (size: 20 x 25 cm) in the form of fine droplets using a paint spray gun (Sata-Farbspritz~chn;k GmbH, Ludwigs-burg). After coating, the metal sheet was pre-dried at 80C
for 10 minutes, and a clear coat (coating formulation as described but without pigments) was applied twice as a protec-tive layer.
The resulting metal sheet exhibits a green color of high brilliance at small angles a and ~ (Fig. 1). With increasing angles a and ~, the green color continuously changes to a blue ~dc~ s ~J~
color. Accordingly, on curved surfaces and in the presence of diffuse, non-directional light, a plurality of colors between green and blue are simultaneously visible depending on the viewing angle.
Example 8 Preparation and use of a coating containing mixtures of pig-ments according to the invention -1 g of blue pigment prepared as described in Example 2 and 1 g of red pigment prepared as described in Example 3 were dis-persed in 4 g of thinner for 5 minutes with stirring, further processed as described in Example 7, and sprayed onto a metal sheet provided with a black base. The metal sheet was given a clear coat protective layer as described in Example 7. A
purple color of high brilliance is observed for small values of ~ and ~, which with increasing angles ~ and ~ continuously changes to a turquoise-like color.
Example 9 Determination of the polarization of the reflected light -Upon viewing the metal sheet coated according to Example 4 through a polarizer for left circularly polarized or right circularly polarized light, the reflection color is visible in the first case but the metal sheet appears black in the second case.
Example 10 Incorporation of gree~ pigments in rigid PVC -9o parts by weight of rigid PVC (obtainable from Wacker-B Chemie GmbH, Munich under the name Vinnol H 70 F), 10 parts by weight of bis(2-ethylhexyl) phthalate (Janssen Chimica, 4057 Bruggen 2), 2 parts by weight of Hostastab SnOS 661 (Hoechst e h o7~s ~r~ ~ Q~-k AG, Frankfurt), 1 part of partially saponified ester wax obtained from montan acid (Wachs OP; Hoechst AG, Frankfurt) and 10 parts by weight of green pigments from Example 4 were com-bined and homogenized for 10 minutes at 150C and a friction of S 1:1.1 using a roll. The resulting composition was processed ina press at 170-C to give sheets. The sheets exhibit the same green-blue color effects as the coated metal sheet described in the prec~;ng examples.
Example 11 Incorporation of green pigments in plasticized PVC -100 parts by weight of plasticized PVC (obt~in~hle from Wacker-Chemie GmbH Munich under the name Vinnol P 70), 50 parts by weight of bis(2-ethylhexyl) phthalate, 1 part of barium/zinc B stabilizer (obtainable as Irgastab BZ 505 from Ciba AG, Basle)and 7.5 parts by weight of the green pigments prepared accord-ing to Example 4 were combined, homogenized and poured onto a glass plate. After 10 minutes of gelling in a drying cabinet at 180-C, a transparent film is obtained which exhibits an angle-dependent color effect as described in the prece~;ng examples.
~ > o7'~s ~r~ k
Claims (11)
1. A pigment whose color depends on the viewing angle, which comprises oriented three-dimensionally crosslinked support-free substances of liquid-crystalline structure having a chiral phase and, optionally dyes and pigments, wherein said optional dyes and pigments do not serve as a base for the oriented three-dimen-sionally crosslinked liquid-crystalline substances having a chiral phase.
2. A pigment as claimed in claim 1, wherein the oriented three-dimensionally crosslinked substances of liquid-crystalline structure having a chiral phase are organosiloxanes in which the number of polymerizable groups is at least two.
3. A pigment as claimed in claim 2, wherein the oriented three-dimensionally crosslinked substances of liquid-crystalline structure having a chiral phase, consists of a mixture of organosiloxanes.
4. A pigment as claimed in claim 1, which contains carbon black as the optional pigment.
5. A process for preparing a pigment as claimed in claim 1, which comprises orienting three-dimensionally crosslinkable substances of liquid-crystalline structure having a chiral phase, optionally admixing further pigments and/or dyes, crosslinking the liquid crystalline structure three-dimen-sionally and comminuting to the desired particle size.
6. A pigment as claimed in claim 1, wherein the pigment has a thickness of 1 to 100 µm and a diameter of 1 to 10,000 µm.
7. The process as claimed in claim 5, wherein the substances, for orientation, are applied to a backing and again removed therefrom before comminution.
8. A pigment as claimed in claim 1, further having at least one substance from the group consisting of phenolic resins, amino resins, alkyd resins, polyvinyl acetate resins, epoxy resins, polyurethane resins, polyethylene resins, chlorinated rubber resins, cyclorubber resins, chlorinated polypropylene, ketone resins, acrylate resins, melamine resins, urea/formaldehyde resins, and phenol/formaldehyde resins.
9. A pigment as claimed in claim 1 further having at least one substance from the group consisting of acrylonitrile/buta-diene/styrene copolymers, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate, cellulose nitrate, cellulose propionate, casein plastics, polyamide, polycar-bonate, polyethylene, polybutylene terephthalate, polymethyl methacrylate, polypropylene, polystyrene, polytetrafluoro-ethylene, polyvinyl chloride, polyvinylidene chloride, poly-urethane, styrene/acrylonitrile copolymers and unsaturated polyester resins.
10. Pigmented paints, coatings, plastics, fiber raw materials, printing inks and cosmetics comprising a pigment as claimed in claim 1.
11. A security marking wherein the marking comprises a pigment as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4240743A DE4240743A1 (en) | 1992-12-03 | 1992-12-03 | Pigments with colors depending on the viewing angle, their production and use |
| DEP4240743.5 | 1992-12-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2110099A1 CA2110099A1 (en) | 1994-06-04 |
| CA2110099C true CA2110099C (en) | 1997-02-04 |
Family
ID=6474346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002110099A Expired - Fee Related CA2110099C (en) | 1992-12-03 | 1993-11-26 | Pigments whose color depends on the viewing angle, their preparation and use |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5362315A (en) |
| EP (1) | EP0601483B1 (en) |
| JP (1) | JP2519018B2 (en) |
| KR (1) | KR0134948B1 (en) |
| AT (1) | ATE128481T1 (en) |
| CA (1) | CA2110099C (en) |
| DE (2) | DE4240743A1 (en) |
| DK (1) | DK0601483T3 (en) |
| ES (1) | ES2077462T3 (en) |
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| DE3110048A1 (en) * | 1981-03-16 | 1982-09-30 | Consortium für elektrochemische Industrie GmbH, 8000 München | "COMPOSITIONS CONTAINING LIQUID CRYSTALLINE PHASES BASED ON CYCLIC ORGANOPOLYSILOXANS, THEIR PRODUCTION AND THEIR USE" |
| DE3119459A1 (en) * | 1981-05-15 | 1982-12-09 | Consortium für elektrochemische Industrie GmbH, 8000 München | LIQUID-CRYSTALLINE PROPERTIES WITH CROSS-LINKED ORGANOPOLYSILOXANES |
| US4780383A (en) * | 1985-02-27 | 1988-10-25 | Armstrong World Industries, Inc. | Optical storage system having expanded capacity |
| DE3830592A1 (en) * | 1988-09-08 | 1990-04-12 | Consortium Elektrochem Ind | (METH) ACRYLOXY GROUPS CONTAINING LIQUID CRYSTALLINE POLYORGANOSILOXANES |
| ATE112586T1 (en) * | 1989-02-13 | 1994-10-15 | Akzo Nobel Nv | LIQUID CRYSTAL PIGMENT, METHOD OF MANUFACTURE AND USE IN CLOTHING. |
-
1992
- 1992-12-03 DE DE4240743A patent/DE4240743A1/en not_active Withdrawn
-
1993
- 1993-11-22 US US08/155,353 patent/US5362315A/en not_active Expired - Fee Related
- 1993-11-26 CA CA002110099A patent/CA2110099C/en not_active Expired - Fee Related
- 1993-11-29 KR KR1019930025716A patent/KR0134948B1/en not_active IP Right Cessation
- 1993-12-01 JP JP5302021A patent/JP2519018B2/en not_active Expired - Lifetime
- 1993-12-02 AT AT93119438T patent/ATE128481T1/en not_active IP Right Cessation
- 1993-12-02 DE DE59300677T patent/DE59300677D1/en not_active Revoked
- 1993-12-02 DK DK93119438.5T patent/DK0601483T3/en active
- 1993-12-02 EP EP93119438A patent/EP0601483B1/en not_active Revoked
- 1993-12-02 ES ES93119438T patent/ES2077462T3/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2519018B2 (en) | 1996-07-31 |
| US5362315A (en) | 1994-11-08 |
| DE4240743A1 (en) | 1994-06-09 |
| DK0601483T3 (en) | 1995-12-04 |
| EP0601483B1 (en) | 1995-09-27 |
| DE59300677D1 (en) | 1995-11-02 |
| KR0134948B1 (en) | 1998-04-18 |
| CA2110099A1 (en) | 1994-06-04 |
| KR940014735A (en) | 1994-07-19 |
| EP0601483A1 (en) | 1994-06-15 |
| ES2077462T3 (en) | 1995-11-16 |
| ATE128481T1 (en) | 1995-10-15 |
| JPH06220350A (en) | 1994-08-09 |
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| MKLA | Lapsed |